Arylamino anthraquinone dyestuffs and a process for their manufacture



Patented Apr. 6, 1943 UNITEDSTATES PATENT OFFICE ARYLAMINO ANTHRAQUINONEDYESTUFFS AND A PROCESS FOR THEIR MANUFAC- TURE Ernst Gutzwiller, Basel,Switzerland, assignor to the firm of Sandoz Ltd., Fribourg, SwitzerlandN Drawing. Application December 20, 1940, Se-

rial No. 371,049.. In Switzerland December 20,

4 Claims. (Cl. 260-374) wherein X represents methyl or ethyl, Yrepresents methyl, ethyl or halogen and Z represents hydrogen or methyl,with such 6-halogen anthraquinone derivatives that contain in the 1- and4-position two groups replaceable by an aromatic amine and in which the7-position is substituted by hydrogen or halogen.

The aromatic amines useful for the production of the new anthraquinonedyestuffs are for example 1-amino-2 :4 G-trimethylbenzene, l-amino-2G-dimethylbenzene, 1-amino-2 :4-dimethyl- G-bromobenzene,1-amino-6-ethyl-2:-dimethylbenzene and the like.

The anthraquinone derivatives which can be used in the present processare for example 6- chloroquinizarine, 6 7-dichloroquinizarine, 1 4 :6-trichloranthraquinone, 1-hydroxy-4-amino-6- chloroor -'7-chloroor6:7-dichloroanthraqui none and the leuco-derivatives of these compounds.

The condensation of the anthraquinone derivatives with the aromaticbases of the above cited configuration is generally carried out inpresence of a solvent and a catalyst at temperatures between 50 and 250C., and in an open or in a closed vessel. As suitable solvents thefollowing ones, or mixtures thereof, can be used: water, ethanol,methanol and other aliphatic alcohols, chlorobenzene, nitrobenzene,dimethylaniline, phenol, glacial acetic acid and the o-o-disubstitutedbases themselves when they are used in excess.

As catalyst generally boric acid or finely divided copper or coppersalts may be used, but it is also possible to carry out the condensationin absence of such a catalyst.

Sometimes it is advantageous to carry out the condensation in an inertatmosphere, for example in nitrogen or carbon dioxide atmosphere,preferably under addition to the reaction mixture of acid bindingagents, such as sodium-, potassiumor ammonium-acetate, sodiumorpotassium-carbonate or -bicarbonate, soap and the like.

In order to prepare water soluble dyestufis from water-insolublecondensation products the latter are sulphonated with sulphuric acid orfuming sulphuric acid of appropriate concentration of S03 or withchlorosulphonic acid, whereby one or more sulphonic acid groups may beintroduced into the molecule.

The dyestufis prepared according to the present process are valuableacid dyestuffs dyeing wool and natural silk fast blue tints showing agreenish shade in the artificial light.

The following examples, without being limitative, illustrate the presentinvention, the parts being by weight:

v Example 1 10 parts of 6-chloroquinizarine, '15 parts ofleuco-G-chloroquinizarine, parts of mesidine,-

CH3 I m om co sosn H3 NH -oH3 SOaH CH3 By replacing the6-chloroquinizarine (or its leuco-derivative) by 6-bromoquinizarine (orits leuco derivative) the respective brominated dyestuff will beobtained which dyes wool similar shades.

Example 2 20 parts of 1:4:B-trichloranthraquinone, 18 parts ofpotassium-acetate, 0.1 part of copper powder and '70 parts of mesidineare stirred at -180 C. until a test in benzene does not become bluer.The base is then isolated by pouring the reaction mixture into ethanoland sulphonated as above described. A dyestufi will be obtained which isidentical to the dyestuif of Example 1.

Example 3 10 parts of 6:7-dichloroquinizarine, 15 parts ofleuco-6:l-dichloroquinizarine, '75 parts of mesidine, 25 parts ofglacial acetic acid and 7.5 parts of boric acid are stirred in an inertatmosphere at 90-140 C. until the condensation is terminated, and theformed base is isolated in the manner described in Example 1. Onsulphonation with weak oleum a water soluble dyestufi dyeing wool andsilk greenish blue shades of excellent fastness properties will beobtained. It possesses the formula:

halogen atoms are used, the respective dihalogenated bases and dyestufiswill be obtained.

Example 4 10 parts of fi-chloroquinizarine, 15 parts ofleuco-6-ch1oroquinizarine, 75 parts of vie-mxylidine, 25 parts ofglacial acetic acid and .5 parts of boric acid are condensed and Workedup in the manner described in Example 1. The base thus obtained is thensulphonated with weak oleum and yields a dyestufi dyeing wool and silkblue shadesof excellent fastness properties. It possesses the followingformula:

$03K F c CH:

scan CH3 Example 10 parts of fi-chloroquinizarine, parts ofleuco-6-chloroquinizarine, 85 parts of l-amino-2:4-dimethyl-G-chlorobenzene, parts of glacial acetic acid and 8 partsof boric acid are condensed at 90 160 C. in the manner described inExample 1 and sulphonated with weak oleum. The dyestufi thus obtaineddyes Wool blue shades having excellent fastness properties. Itcorresponds to the formula:

SOaH

What I claim is: 1. The anthraquinone dyestuffs of the general formula:

0 o s o H A CH3 3 hal (30/ CH:

OHa

wherein hal stands for a member of the group consisting of chlorine andbromine, A stands for a member of the group consisting of hydrogen,chlorine and bromine and X stands for a member of the group consistingof hydrogen and methyl, said dyestuffs being valuable compounds fordyeing wool and silk in fast blue shades.

2. The anthraquinone dyestufi of the formula 11111 00 O: C 01- 0 v 00 iS0311 CH3 which dyes wool and silk greenish blue fast shades.

The anthraquinone dyestufi" of the formula e IIIHQCH: o0 so H 01- CH3 3which dyes wool and silk greenish blue shades of excellent fastnessproperties.

4. The anthraquinone dyestufi of the formula 803E CH3 which dyes wooland silk blue shades.

ERNST GUTZWILLER

